Stabilization of organic compounds



2 145%? STABILIZATION OF ORGANIC .COMPGUNDS Joseph A. Chenicek, Bensenyille, 111., assignor to Uniyers'al Oil Products Company, Chicago, Ill, a corporation of Delaware i N0 Drawi ppli a i n Ji y 1 1 52 7??! N9- 238 0 C ie sto 4-45% This invention relates to the stabilization of organic 4-.

during shipment, treatmentor use, and undergodiscoloration, fform gums, form sludges or otherwise deteriorate due to various undesirable reactions which may include oxidation, polymerization, condensation, etc. Included among the organic compounds which undergo such deterioration ar'e fuel oil, burner oil, furnace oil, diesel i I fuel, jet fuel, mineral oil, lubricating oil, gasoline, drying oil, greases, rubber, edib le vfats and oils, .acetylenes, and particularly vinyl acetylenes, butadi enes, .isoprenes, styrene and other 'vinyl aromatics, various unsaturated alco- ,hois, acids,ketones,etc. v r

Ihe invention is particularly applicable tothestabilizationof burner oils Iwhich undergo discoloration and form undesirable sediment in storage. Burner: oils are marketed underrvarious trade names such as fuel oil, ,furnace oil, burner oil, dieseltuel, jet fuel etc. and are selected to meet commercial specificationsf It is understood that the term burner oil-"Wis used in the present specification and claims in a generic senseto include hydrocarbon distillateszheavier than gasoline. in general, thesehydrocarbon distillates will have initial .boiling points ranging aslowas300 F. and end boilingpoints which .mayrange up to about 75 0 F.

Discoloration of burner oil is undesirable because marketing of the burneroil is most cases includes a color specification, and, therefore, :it is important that the burner oil does not undergo discoloration in storage. Similarly, the formation of sediment vin burner oil is objectionable because the sediment tends to plug strainers, burner tips, injectors, etc., and-whenus'ed as diesel fuel, tendstoform varnish and sludge in the cylinders of the diesel engine. The sediment referred to'herein is dilferent fromthe solid materialoriginally containedas such in burner oil and referredvto inthc art as B. S. & W. ,The sedimentwith whichthe presentinvention is concernedis not contained in thezburneroil as produced but forms during. storage.

At the present time .burner oils .come primarily from non-destructive distillation of petroleum oil, commercially referred to in the art as straight run distillates, and fromcatalytic and non-catalytic cracking processes, commonly referredtoin the art as cyclestocks. -The term cycle stocks is used because the burner oil is separated from a fraction which is recycled to the cracking process for further conversion therein. Other sources of burner oil may include those produced by the reaction of carbon monoxide with hydrogen, ,e tc. Regardless of the source, many of the burnerv oils are unstable in storageand undergo discoloration and sediment formation. This is particularly true in blends of straight run-petroleum distillates and cracked hydrocarbonoils, particularly catalytically cracked hydrocarbon oils, all being heavier than gasoline.

2,734,057 Patented July 26, 1955 2 Because of the increased amount of cycle stocks available, many refiners are marketing blended burner oils and, therefore, require some method of retarding and/or preventing this undesirable deterioration.

In one embodiment the present invention relates to a process for stabilizing an organic compound against deterioration in storage, which comprises adding thereto a l,3 ,5-triazine. I

In a specific embodiment the present invention relates to a process for retarding discoloration of burner oil in storage, which comprises adding thereto less than about 1% by weight of a l,4-dihydro-l,3, 5 triazine.

In another specific embodiment the present invention relates to a process for retarding sediment formation and discoloration of burner oil in storage which comprises adding thereto fromabout .0.Q00l% to about 1% by weight of .a diamino-.l,4-dihydro-1,3,5-triazine.

In another specific embodiment the present invention relates to a process for retarding sediment formation and discoloration of a blend of straight run petroleum distillate and cracked hydrocarbon oil, both heavier than gasoline, which comprises adding thereto from about 0.001% to about 0.1% by weight of 2-amino-4-n propyl- 6-dodecylphenylamino-lA-dihydro-1,3,5-triazine.

In another embodiment ,the present invention relates to an organic compound tendingto deteriorate in storage, and particularly burner oil, containing, as a retardant of said deterioration, a minor amount of the additive'h'erein setforth.

Intheinterest of simplicity, thefollowing specifications will be directed primarily tothe treatment of burner oil. Howeven itisunderstood that the invention is applicable to the treatment of other organic compounds which undergo deterioration in storage as .hereinbefore set forth. lnaccordancewith the present invention, deterioration .of .the unstable organic compoundis retarded by adding thereto a 1,3,5 triazin e and particularly a hydro- 1,3,5-.triazine including a lA-dihydro-l,3,5:triazine, a 1,2,3,4 tetrahydro-1,3,5-triazine and a hexahydro-1,3,5- triazine, and more particularly a diamino-hydro-triazine andlstillmore particularly a diamino-1,4 dihydro-1,3,5-

tr'iazine.

The 1,3,5,-triazine maybe illustrated bythe following general structures:

/4 4 N? an t? E R-dz (jg-R R J2 LB. \1/

Structure I illustrates a 1,3,5-triazine and R may be selected from the group comprising hydrogen, hydrocarbon groups including, alkyl, aralkyl, aryl, alkylaryl, alkenyl, cycloalkenyl, cycloalkyl, amino, guanylamino, hydrocarbonamino, nitro, nitrohydrocarbon, hydroxy, hydroxyhydrocarbon, etc. Specific compounds of this structure include 2,6 diamino 4-.propyl-l,3,5,-triazine, 2,6-diamino-4-methylphenyl-1,3,5rtriazine, 2,6-diamino- 4 dodecylphenyl 1,3,5 triazine, 2,4-diamino-6-butyl- 1,3,5-triazine, 2,4-diamino-6-dodecylphenyl-1,3,5-triazine, 2-amino-4-propyl-6-phenylamin o- 1 3 ,5 -triazine, 2-amino- 4-butyl-6-dodecylphenylamino-1,3,5-triazine, 2,6-di-octylphenylamino-1,3,5-triazine, 2,6di-dodecylphenylamino-4- propyl-l,3,5-triazine, etc.

The hydro-1,3,5triazines are preferred and particularly the 1,4-dihydro-1,3,5-triazines illustrated in structure II. Here again, R may be selected from the groups hereinbefore set forth. Compounds of this structure include 2 amino 4-phenyl-6-dodecylphenyl-amino-1,4-dihydro- 1,3,5-triazine, 2-amino-4-n-propyl-6-dodecylphenylamino- 1,4 dihydro 1,3,5 triazine, 2-amino-4'isopropyl-6-dodecylphenylamino-1,4-dihydro-1,3,5-triazine, 2-amino-4- butyl 6 dodecylphenylamino-1,4-dihydro-1,3,5-triazine, 2 amino-4-amyl-6-nonylphenylamino-1,4-dihydro-1,3,5- triazine, 2 amino 4 hexyl-6-hexylphenylamino-1,4-dihydro 1,3,5 triazine, 2 amino 4,6-di-dodecylphenylamino-1,4-dihydro-1,3,5-triazine, etc. Other representative compounds include 2,4,6-triamino-1,4-dihydro-1,3,5- triazine, 2,4 diamino-6-octyl-1,4,-dihydro-1,3,5-triazine, 2,4 diamino 6 dodecylphenylamino-l,4-dihydro-1,3,5- triazine, 2,4,6 trihexylamino-1,4-dihydro-1,3,5-triazine, 2,4,6-triphenylamino-1,4-dihydro-1,3,5-triazine, 2,4,6-tridodecylphenylamino-1,4-dihydro-1,3,5-triazine, etc.

Structure III illustrates a 1,2,3,4-tetrahydro-l,3,5-triazine, wherein R may be selected from the group as hereinbefore set forth. Suitable compounds of this structure include 2-amino-1,2,3,4-tetrahydro-1,3,5-triazine, 2-4-diamino-1,2,3,4-tetrahydro-1,3,5-triazine, 2,4,6 triamino- 1,2,3,4 tetrahydro-1,3,5-triazine, 3,4-tetrahydro-1,3,5-triazine, 2-amino-4-propyl-6-phenyl- 1,2,3,4-tetrahydro 1,3,5 triazine, 2-amino-4-propyl-6- phenylamino-1,2,3,4-tetrahydro-1,3,5-triazine, 2-amino-4- propyl 6 dodecylphenylamino-1,2,3,4-tetrahydro-1,3,5- triazine, 2,4,6 tributyl-1,2,3,4-tetrahydro-1,3,5-triazine, 2,4,6-tributylamino-1,2,3,4-tetrahydro-1,3, 5 -triazine, 2,6- diamino 4-dodecylphenylamino-1,2,3,4tetrahydro-1,3,5- triazine, etc.

Structure IV illustrates a hexahydro-1,3,5-triazine and, here again, the R groups may be selected in the manner as hereinbefore set forth. Representative compounds of this structure include 2,4,6-triamino-hexahydro-1,3,5-triazine, 2-amino-4-butyl-6-octylamino-hexahydro-1,3,5-triazine, 2-amino-4-propyl-6-dodecylphenylamino-hexahydro-1,3,5-triazine, 2,4-di-dodecylphenylamino-hexahydro- 1,3,5 triazine, 2,4 di dodecylphenylamino-6-rnethylhexahydro-1,3,5-triazine, 2,4 diamino-S-dodecylphenylamino hexahydro 1,3,5-triazine, 2,4-diamino-6-octylamino-hexahydro-1,3,5-triazine, etc.

It is understood that the additive of the present invention may comprise the specific compounds named herein alone or in admixture with various isomers thereof. Furthermore, it is understood that the various additives which may be utilized in accordance with the present invention are not necessarily equivalent for use in the stabilization of the different organic compounds which may be treated in accordance with the present invention. Furthermore, it is understood that the particular additive to be used should be selected so as to meet the specific requirements of the particular material being stabilized. For example, in the treatment of burner oil, the R groups should be selected so that the additive contains a total of from about 10 to about 30 carbon atoms per molecule in order that the additive will not be too volatile, will be readily soluble, etc. It is appreciated that the particular selection of the substituent groups will depend upon the particular organic material in which the additive is to be employed.

The 1,3,5-triazines of the present invention may be prepared in any suitable manner. For example, Z-amino, 4,6-dialkyl-1,3,5-triazine may be prepared by the reaction of nitriles with guanidine. 2,6-diamino-4-alkyl- 1,3,5-triazine may be prepared by the reaction of alkylbiguanides with acylating agents in the presence of alkali.

2-amino-4-propyl-1,2,- 7

2-amino-4-methyl-6-hydroxyl-1,3,5-triazine may be prepared by the condensation of acetylurethane and guanidine.

1,4-dihydro-1,3,5-triazines may be prepared by the reaction of biguanide with aldehydes. When substituted dihydro-1,3,5-triazines are desired, the biguanide is suitably substituted. Thus, in the preparation of the preferred 2-arnino-4-n-propyl-6-dodecylphenylamino-1,4-dihydro-1,3,5-triazine, dodecylphenyl biguanide is reacted with butyraldehyde, the reaction being readily effected by merely boiling equimolecular quantities of the components or solutions thereof, with constant water separation. 2-amino-4-hydroxy--dodecylphenylamino-1,3,5- triazine may be prepared by the reaction of dodecylphenyl biguanide with urea. Hexahydro-1,3,5-triazines may be prepared by the reaction of moist aldehyde-ammonia and guanidine nitrate at 70-75 C.

As hereinbefore set forth, the novel process of the present invention is particularly applicable for the stabilization of burner oils. However, it is understood that this process also may be used for the stabilization of other organic materials which undergo deterioration in storage. Specifically, the present invention may be utilized for the stabilization of gasoline and more particularly unsaturated gasolines, including cracked gasoline, polymer gasoline, etc., as well as to the treatment of aviation gasoline which tends to undergo deterioration due to the addition of tetraethyl lead fluid or other components in the gasoline. Furthermore, the process may be used for the stabilization of petroleum waxes, adhesives, rubber, greases, etc., as well as animal and vegetable fats and oils including, linseed oil, menhaden oil, cod liver oil, castor oil, olive oil, rapeseed oil, coconut oil, palm oil, corn oil, sesame oil, peanut oil, babassu oil, butter, fat, lard, beef tallow, waxes, etc.

The additive of the present invention is generally added to the organic material in an amount of less than about 1% by weight and more generally within the range of from about 0.0001% to about 1% and preferably of from about 0.001% to about 0.1% by weight. It is understood that these additives may be used alone or in conjunction with other additives employed for specific purposes depending upon the particular organic material being treated. For example, in the treatment of burner oil, these additives may be used in conjunction with antioxidants which may comprise aliphatic amines, amino-alcohols, imidazolines, etc., metal deactivators, dyes, detergents, drying agents, etc. When used in gasoline, the additive may be employed along with antioxidants, particularly of the phenolic, amino phenolic of phenylene diamine type, metal deactivators, dyes, anti-knock agents including tetraethyl lead, etc. When used in edible fats and oils, the additive may be employed along with synergists such as citric acid, ascorbic acid, phosphoric acid, etc.

In most cases, the additive of the present invention will be liquid at atmospheric conditions and, therefore, may be readily incorporated in the organic material to be stabilized. When desired, the additive may be utilized in a suitable solvent, including hydrocarbons, alcohols, glycols, ethers, ketones, etc., and in such cases, the additive may be prepared as a solution in the solvent and marketed in this manner alone or along with any other component to be included in the mixture as hereinbefore set forth.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I This example illustrates the beneficial efiects of the preferred 2-amino-4-n-propyl-fi-dodecylphenylamino-1,4- dihydro-1,3,5-triazine in retarding discoloration of a burner oil. The additive was prepared by the reaction of dodecylphenyl biguanide with butyraldehyde in the manner hereinbefore set forth.

Discoloration of the burner oil containing various additives was determined in an. accelerated test, which avoids the necessity of running long time storage tests in order to determine the effect of the various additives. In other runs it has been found that this accelerated test correlates quite satisfactorily with the long time storage test and, therefore, gives a true picture of the stability of the fuel. The samples of the fuel oil were stored at 100 C. for 20 hours. The color was determined in a Lumitron, Model 402E, spectrophotometer, and the data are reported as the per cent transmittance. It is apparent that the per cent transmittance is inversely proportional to discoloration, and that high per cent transmittance means low discoloration.

2 amino 4 n propyl 6 dodecylphenylamino 1,4- dihydro-1,3,5-triazine was added in an amount of 0.008% by weight to a sample of the burner oil. This sample, together with a sample not containing this additive, were tested in the accelerated test described above. The results are shown in the following table:

TABLE 1 Percent Additive Transmittance None 2-amino-4-n-propyl-G-dodecylphenylam ihydr 5-triazine 80 It will be noted that the sample not containing the additive became very dark in color after aging at 100 C. for hours. On the other hand, the sample containing the 1,4-dihydro-1,3,5-triazine still had a per cent transmittance of 80 after aging in the same manner.

Example 11 The additive in this example comprised 2-amino-4- penhyl 6 dodecylphenylamino 1,4 dihydro 1,3,5- triazine and was added in a concentration of 0.006% by weight to another sample of the burner oil described in Example I. When tested in the same manner, the burner oil containing this additive had a per cent transmittance of 74, in contrast to the zero per cent transmittance for the sample not containing this additive. Here again it will be noted that the additive of the present invention served to effectively retard discoloration of the burner oil.

Example III This example illustrates the beneficial effects obtained by the use of the additive of the present invention in retarding sediment formation in burner oil. The burner oil used in this example was the same as that described in Example I. The tendency to form sediment was determined by an accelerated test involving exposure of the sample to light from a carbon arc lamp for 90 minutes under controlled conditions. he sediment formed was determined by filtration of the sample after exposure.

0.01% by Weight of the additive was added to one sample of the burner oil and, after testing in the manner described herein, the sample containing additive and the sample without additive had the following sediment contents:

TABLE 2 Sediment, mg. per 100 ml.

Additive None 2. 2 2-a1nino-4-n-propyl-6-dodecylphenylamino-1,4-dihydro-1,3,

5-triazine O. 7

Example I V 2 amino 4 orthohydroxyphenyl 6 dodecylphenylamino-1, 4-dihydro-1,3,5-triazine, prepared by the-reaction of salicylaldehyde with dodecylphenylbiguanid e, may be used in a concentration of 0.1% to effect stabilization of burner oil. When tested in the manner described in Example J, the sample containing the additive will have a per cent transmittance of 81, whereas the sample of fuel oil without the additive had a per cent transmittance of 0.

Example V As hereinbefore set forth, the accelerated aging test correlates very satisfactorily with long time storage tests. This example illustrates the results obtained in storage tests of different samples of a burner oil, one sample containing the additive described in Example I and the other sample not containing this additive. The results to-date of these storage tests are indicated in the following table:

I claim as my invention:

1. Burner oil tending to undergo discoloration in storage, containing, as a retardant of said discoloration, from about 0.0001% to about 1% by weight of a 2-amino-4- alkyl--alkylphenylamino-l,4-dihydro-1,3,5-triazine.

2. Burner oil tending to undergo discoloration in storage, containing, as a retardant of said discoloration, from about 0.001% to about 0.1% by weight of 2-amino-4-npropyl-6-dodecylphenylamino-l,4-dihydro-1,3,5-triazine.

3. A blend of straight run petroleum distillate and cracked hydrocarbon oil, both heavier than gasoline, containing, as a retardant of sediment formation and discoloration in storage, from about 0.001% to about 0.1% by weight of 2-arnino-4-n-propyl-6-dodecylphenylamino- 1,4-dihydro-1,3,5-triazine.

4. A hydrocarbon oil heavier than gasoline and normally subject to sediment formation in storage containing an amino-substituted 1,3,5-triazine in suflicient amount to retard said sediment formation.

5. A hydrocarbon oil heavier than gasoline and normally subject to sediment formation in storage containing an amino-substituted, hydro-1,3,5-triazine in sufficient amount to retard said sediment formation.

6. A hydrocarbon oil heavier than gasoline and normally subject to sediment formation in storage containing an amino-substituted, 1,4-dihydro-1,3,5-triazine in sufiicient amount to retard said sediment formation.

7. A hydrocarbon oil subject to sediment formation in storage containing a 2-amino-4-alkyl-6-alkylphenylarnino- 1,4-dihydro-1,3,5-triazine in sufficient amount to retard said sediment formation.

8. A hydrocarbon oil subject to sediment formation in storage containing Z-amino-4-n-propyl-6-dodecylphenylamino-1,4-dihydro-1,3,5-triazine in sufficient amount to retard said sediment formation.

9. A hydrocarbon oil heavier than gasoline and normally tending to deteriorate in storage, containing, in sufficient amount to retard said deterioration, a 2,6-diaminodihydro-1,3,5-triazine.

10. A hydrocarbon oil heavier than gasoline and normally tending to deteriorate in storage, containing, in sufficient amount to retard said deterioration, a 2,6-diaminotetrahydro-1,3,5-triazine.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS Burke Dec. 8, 1942 Oldham Feb. 2, 1943 Thurston June 8, 1943 Schmidt et a1 Aug. 3, 1943 Griin Mar. 16, 1948 Nuun, Jr Oct. 18, 1949 8 OTHER REFERENCES Chemical Abstracts, vol. 27 (1933), page 956. (Copy in Scientific Library.)

Chemical Abstracts, vol. 28 (1934), page 5313. (Copy in Scientific Library.) 

1. BURNER OIL TENDING TO UNDERGO DISCOLORAION IN STORAGE, CONTAINING, AS A RETARDENT OF SAID DISCLORATION, FROM ABOUT 0.0001% TO ABOUT 1% BY WEIGHT OF A 2-AMINO-4ALKYL-6-ALKYLPHENLAMINO-1,4-DIHYDRO-1,3,5-TRIAZINE. 